Physics: Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time

Junrong Zheng, Kyungwon Kwak, John Asbury, Xin Chen, Ivan R. Piletic, M. D. Fayer

Research output: Contribution to journalArticle

352 Citations (Scopus)

Abstract

In general, the formation and dissociation of solute-solvent complexes have been too rapid to measure without disturbing the thermal equilibrium. We were able to do so with the use of two-dimensional infrared vibrational echo spectroscopy, an ultrafast vibrational analog of two-dimensional nuclear magnetic resonance spectroscopy. The equilibrium dynamics of phenol complexation to benzene in a benzene-carbon tetrachloride solvent mixture were measured in real time by the appearance of off-diagonal peaks in the two-dimensional vibrational echo spectrum of the phenol hydroxyl stretch. The dissociation time constant τd for the phenol-benzene complex was 8 picoseconds. Adding two electron-donating methyl groups to the benzene nearly tripled the value of τd and stabilized the complex, whereas bromobenzene, with an electron-withdrawing bromo group, formed a slightly weaker complex with a slightly lower τd. The spectroscopic method holds promise for studying a wide variety of other fast chemical exchange processes.

Original languageEnglish
Pages (from-to)1338-1343
Number of pages6
JournalScience
Volume309
Issue number5739
DOIs
Publication statusPublished - 2005 Aug 26
Externally publishedYes

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Physics
Benzene
Hot Temperature
Phenol
Chemical Phenomena
Electrons
Carbon Tetrachloride
Hydroxyl Radical
Spectrum Analysis
Magnetic Resonance Spectroscopy

ASJC Scopus subject areas

  • Medicine(all)
  • General

Cite this

Physics : Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time. / Zheng, Junrong; Kwak, Kyungwon; Asbury, John; Chen, Xin; Piletic, Ivan R.; Fayer, M. D.

In: Science, Vol. 309, No. 5739, 26.08.2005, p. 1338-1343.

Research output: Contribution to journalArticle

Zheng, Junrong ; Kwak, Kyungwon ; Asbury, John ; Chen, Xin ; Piletic, Ivan R. ; Fayer, M. D. / Physics : Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time. In: Science. 2005 ; Vol. 309, No. 5739. pp. 1338-1343.
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